Hexacoordinated group-14 elements with phosphorus donor ligands: syntheses and stuctures of Me2E[C(E = PMe2)2]2 (E = Si, Ge, Sn)

Hans H. Karsch; Brigitte Deubelly; Ursula Keller; Fritz Bienlein; Roland Richter; Peter Bissinger; Maximilian Heckel; Gerhard Müller

doi:10.1002/cber.19961290705

Hexacoordinated group-14 elements with phosphorus donor ligands: syntheses and stuctures of Me₂E[C(E = PMe₂)₂]₂ (E = Si, Ge, Sn)

Hans H. Karsch, Brigitte Deubelly, Ursula Keller, Fritz Bienlein, Roland Richter, Peter Bissinger, Maximilian Heckel, Gerhard Müller

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Abstract

The dimethyl group-14 element dihalides Me₂EX₂ (E = Si, Ge, Sn; X = Cl or Br) react with two equivalents of Li[C(PMe₂)₂(SiMe₃)] to give the cjs-hexacoordinated complexes Me₂)₂(SiMe₃)]₂ (E = Si: 2a, E = Ge: 2b, E = Sn: 2c), which were characterized spectroscopically and by means of X-ray structure determinations. Whereas 2 a and 2b are isotypic and crystallize in the space group P2_1/c, 2c crystallizes in the space group C2/c with crystaliographic C₂(2) molecular symmetry. In ail cases the diphosphanylmethanide ligands bind in an unisobidentate fashion. For compound 2c, this still can be attributed to the trans influence of the methyl group, but in 2a and 2b clearly borderline cases between hexa- and tetracoordination are found. Compound 2b (E = Ge) is much more on the side of tetracoordination than 2a, thus underlining the importance of small polarity differences for the actual coordination number achieved in compounds with relatively unpolar bonds.

Original language	English
Pages (from-to)	759-764
Number of pages	6
Journal	Chemische Berichte
Volume	129
Issue number	7
DOIs	https://doi.org/10.1002/cber.19961290705
State	Published - 1996

Keywords

Germanium compounds
Hexacoordination
Phosphanylmethanide ligands
Silicon compounds
Tin compounds

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@article{e84ab418fc3b4d2eb19ae7818d9c92a8,

title = "Hexacoordinated group-14 elements with phosphorus donor ligands: syntheses and stuctures of Me2E[C(E = PMe2)2]2 (E = Si, Ge, Sn)",

abstract = "The dimethyl group-14 element dihalides Me2EX2 (E = Si, Ge, Sn; X = Cl or Br) react with two equivalents of Li[C(PMe2)2(SiMe3)] to give the cjs-hexacoordinated complexes Me2)2(SiMe3)]2 (E = Si: 2a, E = Ge: 2b, E = Sn: 2c), which were characterized spectroscopically and by means of X-ray structure determinations. Whereas 2 a and 2b are isotypic and crystallize in the space group P21/c, 2c crystallizes in the space group C2/c with crystaliographic C2(2) molecular symmetry. In ail cases the diphosphanylmethanide ligands bind in an unisobidentate fashion. For compound 2c, this still can be attributed to the trans influence of the methyl group, but in 2a and 2b clearly borderline cases between hexa- and tetracoordination are found. Compound 2b (E = Ge) is much more on the side of tetracoordination than 2a, thus underlining the importance of small polarity differences for the actual coordination number achieved in compounds with relatively unpolar bonds.",

keywords = "Germanium compounds, Hexacoordination, Phosphanylmethanide ligands, Silicon compounds, Tin compounds",

author = "Karsch, {Hans H.} and Brigitte Deubelly and Ursula Keller and Fritz Bienlein and Roland Richter and Peter Bissinger and Maximilian Heckel and Gerhard M{\"u}ller",

year = "1996",

doi = "10.1002/cber.19961290705",

language = "English",

volume = "129",

pages = "759--764",

journal = "Chemische Berichte",

issn = "0009-2940",

publisher = "John Wiley and Sons Ltd",

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TY - JOUR

T1 - Hexacoordinated group-14 elements with phosphorus donor ligands

T2 - syntheses and stuctures of Me2E[C(E = PMe2)2]2 (E = Si, Ge, Sn)

AU - Karsch, Hans H.

AU - Deubelly, Brigitte

AU - Keller, Ursula

AU - Bienlein, Fritz

AU - Richter, Roland

AU - Bissinger, Peter

AU - Heckel, Maximilian

AU - Müller, Gerhard

PY - 1996

Y1 - 1996

N2 - The dimethyl group-14 element dihalides Me2EX2 (E = Si, Ge, Sn; X = Cl or Br) react with two equivalents of Li[C(PMe2)2(SiMe3)] to give the cjs-hexacoordinated complexes Me2)2(SiMe3)]2 (E = Si: 2a, E = Ge: 2b, E = Sn: 2c), which were characterized spectroscopically and by means of X-ray structure determinations. Whereas 2 a and 2b are isotypic and crystallize in the space group P21/c, 2c crystallizes in the space group C2/c with crystaliographic C2(2) molecular symmetry. In ail cases the diphosphanylmethanide ligands bind in an unisobidentate fashion. For compound 2c, this still can be attributed to the trans influence of the methyl group, but in 2a and 2b clearly borderline cases between hexa- and tetracoordination are found. Compound 2b (E = Ge) is much more on the side of tetracoordination than 2a, thus underlining the importance of small polarity differences for the actual coordination number achieved in compounds with relatively unpolar bonds.

AB - The dimethyl group-14 element dihalides Me2EX2 (E = Si, Ge, Sn; X = Cl or Br) react with two equivalents of Li[C(PMe2)2(SiMe3)] to give the cjs-hexacoordinated complexes Me2)2(SiMe3)]2 (E = Si: 2a, E = Ge: 2b, E = Sn: 2c), which were characterized spectroscopically and by means of X-ray structure determinations. Whereas 2 a and 2b are isotypic and crystallize in the space group P21/c, 2c crystallizes in the space group C2/c with crystaliographic C2(2) molecular symmetry. In ail cases the diphosphanylmethanide ligands bind in an unisobidentate fashion. For compound 2c, this still can be attributed to the trans influence of the methyl group, but in 2a and 2b clearly borderline cases between hexa- and tetracoordination are found. Compound 2b (E = Ge) is much more on the side of tetracoordination than 2a, thus underlining the importance of small polarity differences for the actual coordination number achieved in compounds with relatively unpolar bonds.

KW - Germanium compounds

KW - Hexacoordination

KW - Phosphanylmethanide ligands

KW - Silicon compounds

KW - Tin compounds

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DO - 10.1002/cber.19961290705

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Hexacoordinated group-14 elements with phosphorus donor ligands: syntheses and stuctures of Me₂E[C(E = PMe₂)₂]₂ (E = Si, Ge, Sn)

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